7-aminozolo[1,5-a]pyrimidines and fungicides containing these

ABSTRACT

7-Aminoazolo[1,5-a]pyrimidines of the formula    &lt;IMAGE&gt;  I  where R1 is alkyl or aralkyl, R2 and R3 are each hydrogen or alkyl, and A is nitrogen or CR4, where R4 is hydrogen, alkyl or halogen, and fungicides containing these compounds.

The present invention relates to novel 7-aminoazolo[1,5-a]pyrimidines,processes for their preparation and fungicides containing thesecompounds.

It has been disclosed that 7-aminoazolo[1,5-a]pyrimidines possesspharmacological properties (French Pat. No. 2,448,542, East German Pat.Nos. 99,794 and 55,956, and J. pharm. Soc. Japan 84 (1964), 1113-1118).

We have found that novel 7-aminoazolo[1,5-a]pyrimidines of the formula##STR2## where

R¹ is alkyl which is unsubstituted or substituted by alkoxy or halogenor is aralkyl which is unsubstituted or substituted in the aryl moietyby alkyl, alkoxy or halogen,

R² and R³ are each hydrogen or alkyl, and

A is nitrogen or CR⁴, where

R⁴ is hydrogen, alkyl or halogen, have a good fungicidal action, inparticular against phycomycetes.

R¹ is, for example, C₄ -C₁₈ -alkyl, eg. C₄ -C₈ -alkyl, which isunsubstituted or substituted by fluorine, chlorine, bromine, or C₁ -C₁₈-alkoxy, or is aralkyl where alkyl is of 1 to 12 carbon atoms, eg.benzyl, p-butylbenzyl or 3-phenylpropyl, which can be substituted in thearyl moiety by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, fluorine, chlorine orbromine.

R², R³ and R⁴ are each, for example, hydrogen or C₁ -C₄ -alkyl, eg.methyl, and R⁴ may furthermore be, for example, chlorine or bromine.

Alkyl, or the alkyl moiety of an alkoxy group is, depending on thestated number of carbon atoms, methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl or an isomerof one of these.

We have furthermore found that 7-aminoazolo[1,5-a]pyrimidines of theformula I are obtained if a substituted , β-keto ester of the formula II##STR3## where R¹ and R² have the above meanings and R⁵ is a lower alkylradical, is reacted with an aminoazole of the formula III ##STR4## whereA, R³ and R⁴ have the above meanings, to give a condensate of theformula V ##STR5## where R¹, R², R³ and A have the above meanings, thiscondensate is subjected to a halogenation reaction in which the hydroxylgroup is replaced by halogen, and the product is reacted with ammonia.

The β-keto esters can be prepared as described in Organic SynthesisColl. Vol. 1, page 248.

The reaction of the substituted β-keto esters of the formula II with theaminoazoles of the formula III can be carried out in the presence orabsence of a solvent. It is advantageous to use a solvent which issubstantially inert towards the starting materials and in which thelatter are partially or completely soluble. Particularly suitablesolvents are alcohols, such as ethanol, propanols, butanols, glycols,glycol monoethers or diethylene glycols or their monoethers, amides,such as dimethyl formamide, diethyl formamide, dibutyl formamide orN,N-dimethylacetamide, lower alkanoic acids, such as formic acid, aceticacid or propionic acid, and mixtures of these solvents with water. Thereaction temperatures are from 50° to 300° C., preferably from 50° to150° C., when the reaction is carried out in solution.

The condensates of the formula V which are obtained in this manner areprecipitated from the reaction solutions in general in pure form, andare washed with the same solvent or with water, dried, and thenhalogenated with halogenating agents, in particular chlorinating agents,eg. phosphorus chlorides, preferably phosphorus oxytrichloride, at from50° to 150° C., preferably in excess phosphorus oxytrichloride underreflux. After the excess phosphorus oxytrichloride has been evaporated,the residue is treated with ice water, with or without the addition of awater-immiscible solvent. The chlorination product which is isolatedfrom the dry organic phase, if necessary after evaporation of the inertsolvent, is generally very pure; it is then reacted with ammonia in aninert solvent at from 100° to 200° C. to give the novel7-aminoazolo-[1,5-a]pyrimidine. The reaction is preferably carried outunder from 1 to 100 bar, using a 1-10 molar excess of ammonia.

The novel 7-aminoazolo[1,5-a]pyrimidines are isolated as crystallinecompounds which are generally very pure, by evaporating the solvent ifnecessary and then making a paste with water.

We have furthermore found that 7-aminoazolo[1,5-a]pyrimidines of theformula I are obtained if a substituted benzyl cyanide of the formula##STR6## where R¹ and R² have the above meanings, is reacted with anaminoazole of the formula III ##STR7## where A, R³ and R⁴ have the abovemeanings.

The reaction can be carried out in the presence or absence of a solvent.It is advantageous to use a solvent which is substantially inert towardthe starting materials and in which the latter are partially orcompletely soluble. Particularly suitable solvents are alcohols, such asethanol, propanols, butanols, glycols, glycol monoethers or diethyleneglycols or their monoethers, amides, such as dimethylformamide,diethylformamide, dibutylformamide or N,N-dimethylacetamide, loweralkanoic acids, such as formic acid, acetic acid or propionic acid, andmixtures of these solvents with water. The reaction temperatures arefrom 50° to 300° C., preferably from 50° to 150° C., when the reactionis carried out in solution.

The novel 7-aminoazolo[1,5-a]pyrimidines are isolated as crystallinecompounds, which are generally very pure, if necessary after evaporationof the solvent or dilution with water. Where lower alkanoic acids areused as solvents, it is advantageous to neutralize the remainder of thealkanoic acid by adding an aqueous alkali, if necessary after partialevaporation of the alkanoic acid; the novel7-aminoazolo[1,5-a]pyrimidines generally crystallize out in very pureform.

Some of the substituted alkyl cyanides of the formula ##STR8## which arerequired for the preparation of the 7-aminoazolo[1,5-a]pyrimidines areknown; those which are unknown can be prepared by conventional methods,from an alkyl cyanide and a carboxylate with a strong base, eg. analkali metal hydride, an alkali metal amide or a metalalkyl (J. Amer.Chem. Soc. 73, (1951), 3766).

General methods of preparation for the substituted alkyl cyanides of theformula VI

1.5 moles of sodium hydride are introduced into 1 liter of toluene, and1.0 mole of an alkyl cyanide followed by 2.0 moles of a carboxylate arethen added dropwise to the stirred mixture, the temperature increasingto 40°-50° C. Stirring is continued for 2 hours at from 75° to 80° C.,after which the mixture is cooled and 2 liters of water are added. Theaqueous phase is washed twice with 0.2 liters of toluene and acidifiedwith semiconcentrated (about 50% strength by weight) sulfuric acid to pH2, and the substituted alkyl cyanide of the formula VI is then isolatedfrom the aqueous phase.

EXAMPLES 1. Preparation of 7-amino-2,5-dimethyl-6-n-octylpyrazolo[1,5-a]pyrimidine (Compound 2) (a)7-hydroxy-2,5-dimethyl-6-n-octylpyrazolo[1,5-a]pyrimidine

200 g of methyl 2-n-octylacetoacetate and 94 g of3(5)-amino-5(3)-methylpyrazole in 400 ml of n-butanol are refluxed for 5hours. The mixture is cooled, and the product is filtered off undersuction, washed with cold methanol and dried under reduced pressure at60° C. to give 191 g of7-hydroxy-2,5-dimethyl-6-n-octylpyrazolo[1,5-a]pyrimidine of meltingpoint 199° C.

(b) 7-chloro-2,5-dimethyl-6-n-octylpyrazolo[1,5-a]-pyrimidine

190 g of the condensate obtained from (a), in 550 ml of phosphorusoxytrichloride, are refluxed for 1.5 hours, after which the excessphosphorus oxytrichloride is evaporated under reduced pressure and theresidue is stirred with 500 ml of CH₂ Cl₂ and 500 ml of ice water. Theorganic phase is separated off, washed with three times 100 ml of icewater, dried over sodium sulfate and filtered, the solvent is evaporatedunder reduced pressure, and 179 g of7-chloro-2,5-dimethyl-6-n-octylpyrazolo-[1,5-a]pyrimidine are isolatedas a viscous mass.

(c) 7-amino-2,5-dimethyl-6-n-octylpyrazolo[1,5-a]-pyrimidine

179 g of the chloride obtained in b) and 1300 ml of ethanol areintroduced into a 2.5 liter autoclave, 85 g of ammonia are forced in,and the mixture is stirred at 150° C. and under 30 bar for 8 hours. Thereacted mixture is concentrated under reduced pressure, the residue ismade into a paste with 1000 ml of water, and the product is filtered offunder suction and dried under reduced pressure at 70° C. to give 133 gof 7-amino-2,5-dimethyl-6-n-octylpyrazolo-[1,5-a]pyrimidine of meltingpoint 169° C. (Compound 2).

2. Preparation of7-amino-6-n-butyl-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine (Compound 34)(a) 2-acetyl-n-capronitrile

11.7 g (300 millimoles) of powdered sodium amide are introduced into 500ml of liquid ammonia at -60° C., and a mixture of 29.1 g (300millimoles) of n-capronitrile and 26.4 g (300 millimoles) of ethylacetate is then added slowly. Stirring is continued for 2 hours at -60°C., 200 ml of diethyl ether are added, and the mixture is left overnightto warm up to room temperature, gaseous ammonia escaping. First waterand then 50% strength sulfuric acid are added, while cooling with ice,until the pH reaches 5. The ether phase is separated off, the aqueousphase is extracted twice with ether, the combined organic phases aredried and evaporated down, and the remaining oil (40 g; 96% crude yield)is distilled under reduced pressure. The fraction passing over at 52°C./0.4 mbar has a purity higher than 98% according to gaschromatography.

(b) 9.0 g (65 millimoles) of the nitrile from Example 2a and 5.5 g (65millimoles) of 3-amino-1,2,4-triazole in 200 ml of propionic acid arerefluxed for 12 hours, after which the solution is allowed to cool andis then evaporated down to one third of its initial volume. After sometime, a precipitate is formed; this is filtered off, washed with alittle 2N NaOH and water, and recrystallized from ethanol. Yield: 8.6 g(65%), m.p.: 246° C. (Compound 34).

3. Preparation of7-amino-6-n-butyl-2-methyl-5-n-propylpyrazolo[1,5-a]pyrimidine (Compound24) (a) 2-n-butyryl-n-capronitrile

29.1 g (300 millimoles) of n-capronitrile are reacted with 34.8 g (300millimoles) of ethyl n-butyrate, as described in Example 2a. Crudeyield: 98%, yield of pure compound: 50%, bp.: 94°-95° C./0.2 mbar.

(b) 10.1 g (60.5 millimoles) of the nitrile obtained in 3a and 5.80 g(300 millimoles) of 3(5)-amino-5(3)-methylpyrazole are reacted asdescribed in Example 2b. Yield: 5.0 g (34%), mp. (from ethanol): 167° C.(Compound 24).

4. Preparation of7-amino-5-methyl-6-[3-(n-nonyloxy)propyl]-1,2,4-triazolo[1,5-a]pyrimidine(Compound 44) (a) 2-acetyl-5-(n-nonyloxy)-valeronitrile

35.0 g (156 millimoles) of 5-(n-nonyloxy)-valeronitrile in 500 ml ofabsolute tetrahydrofuran are initially taken, in the absence of waterand under an inert gas atmosphere, and the mixture is cooled to -60° C.162 millimoles of n-butyl-lithium in n-hexane are slowly added to thestirred mixture, which is then left for 4 hours at -60° C. A solution of13.1 g (155 millimoles) of dry ethyl acetate in tetrahydrofuran is thenadded dropwise, stirring is continued for 3 hours at -60° C., and themixture is allowed to warm up slowly to room temperature. First waterand then 2N hydrochloric acid are added while cooling with ice, untilthe pH of the solution reaches 4. The organic phase which separates outis isolated, washed with water, dried and evaporated down. The oil whichremains (41 g; 99%) is more than 90% pure according to gaschromatography, and can be reacted without further purification.

(b) 20.0 g (75 millimoles) of the nitrile from Example 4a are reactedwith 6.30 g (75 millimoles) of 3-amino-1,2,4-triazole in 300 ml ofboiling propionic acid for 16 hours. The mixture is cooled, the solutionis separated off from the precipitate, the filtrate is evaporated down,the residue is taken up in water, the solution is extracted severaltimes with dichloromethane, the combined organic phases are dried andevaporated down, and the oily residue is triturated with diethyl etherto give 9.0 g (36%) of a crystalline compound of melting point 167° C.(Compound 44).

5. Preparation of 7-amino-5-methyl-6-[3-(neopentyloxy)-propyl]1,2,4-triazolo[1,5-a]pyrimidine (Compound 38) (a)7-hydroxy-5-methyl-6-[3-(neopentyloxy)-propyl]-1,2,4-triazolo[1,5-a]pyrimidine

22.0 g (90 millimoles) of methyl2-[3-(neopentyloxy)-propyl]-acetoacetate and 7.14 g (84.9 millimoles) of3-amino-1,2,4-triazole in 300 ml of boiling propionic acid are allowedto react for 21 hours. The mixture is cooled and then evaporated down,the residue is stirred into ice water, the solution is neutralized with2N NaOH, and the product is filtered off under suction to give 13.5 g(57%) of colorless crystals of melting point 155°-159° C., which arereacted without further purification.

(b)7-chloro-5-methyl-6-[3-(neopentyloxy)-propyl]-1,2,4-triazolo[1,5-a]pyrimidine

11.5 g (41.4 millimoles) of the product from 5a, in 330 ml of phosphorusoxytrichloride, are refluxed for 8 hours, after which volatilecomponents are distilled off, the oily residue which remains is taken upin dichloromethane, and the solution is washed with saturated sodiumbicarbonate solution, dried and evaporated down to give 10 g (82%) of ayellowish oil which is pure according to thin layer chromatography.

(c) 10.0 g (33.7 millimoles) of the product from 5b are dissolved in 100ml of dioxane, and then reacted with 6.3 g (370 millimoles) of ammoniain an autoclave at 130° C. for 60 hours. After the mixture has beencooled and the pressure let down, the resulting precipitate is filteredoff under suction and taken up in dichloromethane, and the solution iswashed three times with water, dried and evaporated down to give 5.5 g(58%) of a colorless powder (compound 38) of melting point 202° C. Afurther 2.5 g of product can be obtained by evaporating down thefiltrate from the dioxane solution.

For example, the following 7-aminoazolo[1,5-a]pyrimidines can beprepared by the methods described above:

    __________________________________________________________________________     ##STR9##                                                                     No.                                                                              R.sup.1                  R.sup.2                                                                           R.sup.3                                                                           R.sup.4                                                                         A  M.p. (°C.)                    __________________________________________________________________________    1  n-C.sub.4 H.sub.9        CH.sub.3                                                                          CH.sub.3                                                                          H CR.sup.4                                                                         186                                  2  n-C.sub.8 H.sub.17       CH.sub.3                                                                          CH.sub.3                                                                          H CR.sup.4                                                                         169                                  3  n-C.sub.4 H.sub.9CH(C.sub.2 H.sub.5)CH.sub.2                                                           CH.sub.3                                                                          CH.sub.3                                                                          H CR.sup.4                                                                         159                                  4  n-C.sub.8 H.sub.17       CH.sub.3                                                                          H   --                                                                              N  217                                  5  n-C.sub.4 H.sub.9CH(C.sub.2 H.sub.5)CH.sub.2                                                           CH.sub.3                                                                          H   --                                                                              N  228                                  6  C.sub.6 H.sub.5CH.sub.2  CH.sub.3                                                                          CH.sub.3                                                                          H CR.sup.4                                                                         235                                  7  4-t-C.sub.4 H.sub.9C.sub.6 H.sub.4CH.sub.2                                                             CH.sub.3                                                                          CH.sub.3                                                                          H CR.sup.4                                                                         214                                  8  4-t-C.sub.4 H.sub.9 C.sub.6 H.sub.4CH.sub.2                                                            CH.sub.3                                                                          H   --                                                                              N  >280                                 9  C.sub.6 H.sub.5(CH.sub.2).sub.3                                                                        CH.sub.3                                                                          H   --                                                                              N  244                                  10 n-C.sub.5 H.sub.11       CH.sub.3                                                                          H   --                                                                              N  251                                  11 n-C.sub.6 H.sub.13       CH.sub.3                                                                          H   --                                                                              N  237                                  12 n-C.sub.7 H.sub.15       CH.sub.3                                                                          H   --                                                                              N  209                                  13 n-C.sub.5 H.sub.11       CH.sub.3                                                                          CH.sub.3                                                                          --                                                                              N  193                                  14 n-C.sub.6 H.sub.13       CH.sub.3                                                                          CH.sub.3                                                                          --                                                                              N  200                                  15 n-C.sub.8 H.sub.17       CH.sub.3                                                                          CH.sub.3                                                                          --                                                                              N  198                                  16 n-C.sub.4 H.sub.9        n-C.sub.4 H.sub.9                                                                 H   --                                                                              N  187                                  17 n-C.sub.4 H.sub.9        n-C.sub.4 H.sub.9                                                                 CH.sub.3                                                                          H CR.sup.4                                                                         145                                  18                                                                                ##STR10##               CH.sub.3                                                                          H   --                                                                              N  209                                  19                                                                                ##STR11##               CH.sub.3                                                                          CH.sub.3                                                                          H CR.sup.4                                                                         176                                  20 (H.sub.5 C.sub.2).sub.2CHCH.sub.2                                                                      CH.sub.3                                                                          CH.sub.3                                                                          H CR.sup.4                                                                         178                                  21 n-C.sub.10 H.sub.21      n-C.sub.3 H.sub.7                                                                 H   --                                                                              N  152                                  22 n-C.sub.10 H.sub.21      n-C.sub.3 H.sub.7                                                                 CH.sub.3                                                                          H CR.sup.4                                                                         114                                  23 NC.sub.10 H.sub.21       n-C.sub.4 H.sub.9                                                                 H   --                                                                              N  151                                  24 n-C.sub.5 H.sub.9        n-C.sub.3 H.sub.7                                                                 CH.sub.3                                                                          H CR.sup.4                                                                         167                                  25 n-C.sub.4 H.sub.9        n-C.sub.3 H.sub.7                                                                 H   --                                                                              N  186                                  26 n-C.sub.12 H.sub.25      CH.sub.3                                                                          CH.sub.3                                                                          --                                                                              CR.sup.4                                                                         127                                  27 n-C.sub.12 H.sub.25      CH.sub.3                                                                          H   --                                                                              N  209                                  28 n-C.sub.10 H.sub.21      CH.sub.3                                                                          H   --                                                                              N  207                                  29 n-C.sub.9 H.sub.19       CH.sub.3                                                                          H   --                                                                              N  215                                  30 n-C.sub.6 H.sub.13       CH.sub.3                                                                          CH.sub.3                                                                          H CR.sup.4                                                                         177                                  31 n-C.sub.9 H.sub.19       CH.sub.3                                                                          CH.sub.3                                                                          --                                                                              N  159                                  32 n-C.sub.10 H.sub.21      CH.sub.3                                                                          CH.sub.3                                                                          H CR.sup.4                                                                         146                                  33 4-t-C.sub.4 H.sub.9C.sub.6 H.sub.4CH.sub.2CH(CH.sub.3)                                                 CH.sub.3                                                                          H   --                                                                              N  256                                  34 n-C.sub.4 H.sub.9        CH.sub.3                                                                          H   --                                                                              N  246                                  35 (n-C.sub.3 H.sub.7 )(C.sub.2 H.sub.5)CHCH.sub.2O(CH.sub.2).sub.3                                       CH.sub.3                                                                          CH.sub.3                                                                          H CR.sup.4                                                                         108                                  36 (n-C.sub.3 H.sub.7)(C.sub.2 H.sub.5)CHCH.sub.2O(CH.sub.2).sub.3                                        CH.sub.3                                                                          H   --                                                                              N  149                                  37 t-C.sub.4 H.sub.9 CH.sub.2O(CH.sub.2).sub.3                                                            CH.sub.3                                                                          CH.sub.3                                                                          H CR.sup.4                                                                         134                                  38 t-C.sub.4 H.sub.9CH.sub.2O(CH.sub.2).sub.3                                                             CH.sub.3                                                                          H   --                                                                              N  202                                  39 t-C.sub.4 H.sub.9O(CH.sub.2).sub.4                                                                     CH.sub.3                                                                          CH.sub.3                                                                          H CR.sup.4                                                                         61  (decomposes)                     40 (t-C.sub.4 H.sub.9CH.sub.2)(CH.sub.3)CH(CH.sub.2).sub.2O(CH.sub.2).sub.       5                        CH.sub.3                                                                          H   --                                                                              N  161                                  41 (i-C.sub.4 H.sub.9)(C.sub.2 H.sub.5)CHO(CH.sub.2).sub.3                                                CH.sub.3                                                                          H   --                                                                              N  156                                  42 n-C.sub.8 H.sub.17O(CH.sub.2).sub.3                                                                    n-C.sub.3 H.sub.7                                                                 H   --                                                                              N  97                                   43 i-C.sub.3 H.sub.7(CH.sub.2).sub.3CH(CH.sub.3)(CH.sub.2).sub.2O(CH.sub.2       ).sub.3                  CH.sub.3                                                                          H   --                                                                              N  156                                  44 n-C.sub.9 H.sub.19O (CH.sub.2).sub.3                                                                   CH.sub.3                                                                          H   --                                                                              N  167                                  45 n-C.sub.4 H.sub.9O(CH.sub.2).sub.3                                                                     CH.sub.3                                                                          H   --                                                                              N  180                                  46 n-C.sub.6 H.sub.13O(CH.sub.2).sub.3                                                                    CH.sub.3                                                                          H   --                                                                              N  176                                  47 n-C.sub.9 H.sub.19O(CH.sub.2).sub.3                                                                    CH.sub.3                                                                          CH.sub.3                                                                          H CR.sup.4                                                                         94                                   48 n-C.sub.6 H.sub.13O(CH.sub.2).sub.3                                                                    n-C.sub.3 H.sub.7                                                                 H   --                                                                              N  109                                  49 (n-C.sub.4 H.sub.9)(C.sub.2 H.sub.5)CHCH.sub.2O(CH.sub.2).sub.5                                        CH.sub.3                                                                          H   --                                                                              N  resin                                50 t-C.sub.4 H.sub.9CH.sub.2CH(CH.sub.3)(CH.sub.2).sub.2O(CH.sub.2).sub.3                                 CH.sub.3                                                                          H   --                                                                              N  154                                  51 n-C.sub.4 H.sub.9O(CH.sub.2).sub.3                                                                     CH.sub.3                                                                          CH.sub.3                                                                          H CR.sup.4                                                                         145                                  52 t-C.sub.4 H.sub.9CH.sub.2CH(CH.sub.3)(CH.sub.2).sub.2O(CH.sub.2).sub.3                                 CH.sub.3                                                                          CH.sub.3                                                                          H CR.sup.4                                                                         122                                  __________________________________________________________________________

The novel active ingredients have a strong fungitoxic action onphytopathogenic fungi, especially from the Phycomycetes class. The novelcompounds are therefore suitable for instance for combating Phytophthorainfestans in tomatoes and potatoes, Phytophthora parasitica instrawberries, Phytophthora cactorum in apples, Pseudoperonosporacubensis in cucumbers, Pseudoperonospora humuli in hops, Peronosporadestructor in onions, Peronospora sparsa in roses, Peronospora tabacinain tobacco, Plasmopara viticola in graphes, Plasmopara halstedii insunflowers, Sclerospora macrospora in Indian corn, Bremia lactucae inlettuce, Mucor mucedo in fruit, Rhizopus nigricans in beets, Erysiphegraminis in cereals, Uncinula necator in grapes, Podosphaera leucotrichain apples, Sphaerotheca fuliginea in roses, and Erysiphe cichoriacearumin cucumbers.

The active ingredients are excellently tolerated by plants. Some of theactive ingredients also have curative properties, i.e., the agents maybe applied after infection of the plants by the pathogen and success isstill ensured.

The fungicidal agents contain from 0.1 to 95, and preferably from 0.5 to90, wt % of active ingredient. The application rates depend on the typeof effect desired, and range from 0.1 to 5 kg of active ingredient perhectare.

The novel active ingredients may also be mixed and applied with otheractive ingredients, e.g., herbicides, insecticides, growth regulators,other fungicides and fertilizers. When mixed with other fungicides, thespectrum of fungicidal action is in many cases increased; with a numberof these fungicidal compositions, synergistic effects also occur, i.e.,the fungicidal action of the combination product is greater than theeffect of the individual components added together. Examples offungicides which can be combined with the novel compounds are asfollows:

sulfur

dithiocarbamates and derivatives thereof, such as

ferric dimethyldithiocarbamate

zinc dimethyldithiocarbamate

zinc ethylenebisthiocarbamate

tetramethylthiuram disulfide

manganese-zinc ethylenediamine-bisdithiocarbamate

ammonia complex of zinc-(N,N'-ethylene)-bisdithiocarbamate

and

N,N'-polyethylene-bis-(thiocarbamoyl)-disulfide

ammonia complex of zinc-(N,N'-propylene-bisdithiocarbamate)

and

N,N'-polypropylene-bis-(thiocarbamoyl)-disulfide

nitro derivatives, such as

dinitro-(1-methylheptyl)-phenylcrotonate

2-sec-butyl-4,6-dinitrophenyl-3,5-dimethylacrylate

2-sec-butyl-4,6-dinitrophenylisopropylcarbonate

diisopropyl 5-nitroisophthalate

heterocyclic structures, such as

2-heptadecyl-2-imidazoline acetate

2,4-dichloro-6-(o-chloroanilino)-s-triazine

0,0-diethylphthalimidophosphorothionate

5-amino-1-[bis-(dimethylamino)-phosphynyl]-3-phenyl-1,2,4-triazole

2,3-dicyano-1,4-dithiaanthraquinone

2-thio-1,3-dithio-(4,5-b)-quinoxaline

methyl 1-(butylcarbamoyl)-2-benzimidazole carbamate

2-methoxycarbonylaminobenzimidazole

2-[furyl-(2)]-benzimidazole

2-[thiazolyl-(4)]-benzimidazole

N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide

N-trichloromethylthiotetrahydrophthalimide

N-trichloromethylphthalimide

N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfuric acid diamide

5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole

2-thiocyanomethylthiobenzthiazole

1,4-dichloro-2,5-dimethoxybenzene

4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone

pyridine-2-thio-1-oxide

8-hydroxyquinoline and its copper salt

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin

2-methyl-5,6-dihydro-4-H-pyran-3-carboxanilide

2-methyl-furan-3-carboxanilide

2,5-dimethyl-furan-3-carboxanilide

2,4,5-trimethyl-furan-3-carboxanilide

2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide

N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxamide

2-methyl-benzoic acid anilide

2-iodobenzoic anilide

N-formyl-N-morpholine-2,2,2-trichloroethylacetal

piperazine-1,4-diylbis-(1-(2,2,2-trichloroethyl)-formamide

1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichlorethane

2,6-dimethyl-N-tridecyl-morpholine and its salts

2,6-dimethyl-N-cyclododecyl-morpholine and its salts

N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine

N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-piperidine

1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl-ethyl]-1-H-1,2,4-triazole-1,2,4-triazole

-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-yl-ethyl]-1-H-1,2,4-triazole

N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazol-ylurea

1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone

1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol

alpha-(2-chlorophenyl)-alpha-(4-chlorophenyl)-5-pyrimidinemethanol

5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine

bis-(p-chlorophenyl)-3-pyridinemethanol

1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene

1,2-bis-(3-methoxycarbonyl)-2-thioureido)-benzene

2-cyano-N-(ethylaminocarbonyl)-2-(methoximino)acetamide

and various fungicides, such as

dodecylguanidine acetate

3-[2-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]glutarimide

hexachlorobenzene

D,L-methyl-N-(2,6-dimethylphenyl)-N-(2-furoyl)-alanate

methyl D,L-N-(2,6-dimethylphenyl)-N-(2-methoxyacetyl)-alanate

N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-aminobutyrolactone

methyl DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)-alanate5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine

3-(3,5-dichlorophenyl)-5-methyl-5-methoxymethyl-1,3-oxazolidine2,4-dione

3-(3,5-dichlorophenyl)-1-isopropyl-carbamoylhydantoin

N-(3,5-dichlorophenyl)-1,2-dimethyl-cyclopropane-1,2-dicarboximide.

The novel active ingredients are applied for instance in the form ofdirectly sprayable solutions, powders, suspensions (includinghigh-percentage aqueous, oily or other suspensions), dispersions,emulsions, oil dispersions, pastes, dusts, broadcasting agents, orgranules by spraying, atomizing, dusting, broadcasting or watering. Theforms of application depend entirely on the purpose for which the agentsare being used, but they must ensure as fine a distribution of the novelactive ingredients as possible.

For the preparation of solutions, emulsions, pastes and oil dispersionsto be used direct, mineral oil fractions of medium to high boilingpoint, such as kerosene or diesel oil, further coal-tar oils, and oilsof vegetable or animal origin, aliphatic, cyclic and aromatichydrocarbons carbons such as benzene, toluene, xylene, paraffin,tetrahydronaphthalene, alkylated naphthalenes and their derivatives suchas methanol, ethanol, propanol, butanol, chloroform, carbontetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone,etc., and strongly polar solvents such as dimethylformamide, dimethylsulfoxide, and N-methylpyrrolidone, and water are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes,oil dispersions or wettable powders by adding water. To prepareemulsions, pastes and oil dispersions the ingredients as such ordissolved in an oil or solvent may be homogenized in water by means ofwetting or dispersing agents, adherents or emulsifiers. Concentrateswhich are suitable for dilution with water may be prepared from activeingredient, wetting agent, adherent, emulsifying or dispersing agent andpossibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal andammonium salts of ligninsulfonic acid, naphthalenesulfonic acids,phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkylsulfonates, alkali metal and alkaline earth metal salts ofdibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcoholsulfates, alkali metal and alkaline earth metal salts of fatty acids,salts of sulfated hexadecanols, heptadecanols, and octadecanols, saltsof sulfated fatty alcohol glycol ethers, condensation products ofsulfonated naphthalene and naphthalene derivatives with formaldehyde,condensation products of naphthalene or naphthalenesulfonic acids withphenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylatedisooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol,alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers,alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcoholethylene oxide condensates, ethoxylated castor oil, polyoxyethylenealkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycolether acetal, sorbitol esters, lignin, sulfite waste liquors and methylcellulose.

Powders, dusts and broadcasting agents may be prepared by mixing orgrinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may beprepared by bonding the active ingredients to solid carriers. Examplesof solid carriers are mineral earths such as silicic acid, silica gels,silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loess,clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate,magnesium oxide, ground plastics, fertilizers such as ammonium sulfate,ammonium phosphate, ammonium nitrate, and ureas, and vegetable productssuch as grain flours, bark meal, wood meal, and nutshell meal,cellulosic powders, etc.

Examples of such formulations follow.

I. 90 parts by weight of the compound of Example 1 is mixed with 10parts by weight of N-methyl-alphapyrrolidone. A mixture is obtainedwhich is suitable for application in the form of very fine drops.

II. 20 parts by weight of the compound of Example 2 is dissolved in amixture consisting of 80 parts by weight of xylene, 10 parts by weightof the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleicacid-N-monoethanolamide, 5 parts by weight of the calcium salt ofdodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40moles of ethylene oxide and 1 mole of castor oil. By pouring thesolution into water and uniformly distributing it therein, an aqueousdispersion is obtained.

III. 20 parts by weight of the compound of Example 1 is dissolved in amixture consisting of 30 parts by weight of cyclohexanone, 30 parts byweight of isobutanol, 20 parts by weight of the adduct of 40 moles ofethylene oxide and 1 mole of castor oil. By pouring the solution intowater and finely distributing it therein, an aqueous dispersion isobtained.

IV. 20 parts by weight of the compound of Example 2 is dissolved in amixture consisting of 25 parts by weight of cyclohexanol, 65 parts byweight of a mineral oil fraction having a boiling point between 210° and280° C., and 10 parts by weight of the adduct of 40 moles of ethyleneoxide and 1 mole of castor oil. By pouring the solution into water anduniformly distributing it therein, an aqueous dispersion is obtained.

V. 20 parts by weight of the compound of Example 1 is well mixed with 3parts by weight of the sodium salt ofdiisobutylnaphthalene-alpha-sulfonic acid, 17 parts by weight of thesodium salt of a lignin-sulfonic acid obtained from a sulfite wasteliquor, and 60 parts by weight of powdered silica gel, and triturated ina hammer mill. By uniformly distributing the mixture in water, a sprayliquor is obtained.

VI. 5 parts by weight of the compound of Example 2 is intimately mixedwith 95 parts by weight of particulate kaolin. A dust is obtainedcontaining 5% by weight of the active ingredient.

VII. 30 parts by weight of the compound of Example 1 is intimately mixedwith a mixture consisting of 92 parts by weight of powdered silica geland 8 parts by weight of paraffin oil which has been sprayed onto thesurface of this silica gel. A formulation of the active ingredient isobtained having good adherence.

VIII. 40 parts by weight of the compound of Example 2 is intimatelymixed with 30 parts of the sodium salt of a phenolsulfonicacid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts ofwater to give a stable aqueous dispersion.

IX. 20 parts of the compound of Example 1 is intimately mixed with 2parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of afatty alcohol polyglycol ether, 2 parts of the sodium salt of aphenolsulfonic acid-urea-formaldehyde condensate and 68 parts of aparaffinic mineral oil. A stable oily dispersion is obtained.

The following experiments demonstrate the biological action of the novelcompounds.

EXAMPLE 1 Action on Plasmopara viticola

Leaves of potted vines of the Muller-Thurgau variety were sprayed withaqueous suspensions containing (dry basis) 80% of active ingredient and20% of emulsifier. To assess the duration of action, the plants were setup, after the sprayed-on layer had dried, for 10 days in the greenhouse.Then the leaves were infected with a zoospore suspension of Plasmoparaviticola. The plants were first placed for 16 hours in a watervapor-saturated chamber at 24° C. and then in a greenhouse for 8 days atfrom 20° to 30° C. To accelerate and intensify the sporangiophoredischarge, the plants were then again placed in the moist chamber for 16hours. The extent of fungus attack was then assessed on the undersidesof the leaves.

The results of the experiment show that for instance compounds nos. 1,2, 3, 4, 5, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 25,26, 28, 29, 30, 31 and 32, applied as 0.05 and 0.025% spray liquors, hada better fungicidal action (e.g., 97%) than the prior art activeingredients 7-amino-6-phenyl-(1,2,4-triazolo)-[1,5-a]pyrimidine (A) and7-amino-2-methyl-6-phenyl-pyrazolo-[1,5-a]pyrimidine (B) (e.g., 30%).

EXAMPLE 2 Action of Phytophthora infestans in tomatoes

Leaves of potted tomatoes of the "Groe Fleischtomate" variety weresprayed with aqueous liquors containing (dry basis) 80% of activeingredient and 20% of emulsifier. After the sprayed-on layer had dried,the leaves were infected with a zoospore suspension of Phytophthorainfestans. The plants were then placed for 5 days in a steam-saturatedchamber kept at 16° to 18° C. After this period, the disease had spreadon the untreated control plants to such an extent that the fungicidalaction of the compounds was able to be assessed.

The results of this experiment show that for example compounds nos. 4,5, 10, 11, 13, 14, 15, 16, 18, 19, 20, 21, 25, 29, 33, 36, 40, 41, 48and 49, applied as 0.025% spray liquors, had a better fungicidal action(e.g., 90%) than the prior art active ingredients A andN-trichloromethylthio-tetrahydrophthalimide (e.g., 60%).

We claim:
 1. ##STR12## where R¹ is a .[.C₆ -C₁₈ -alkyl.]. .Iadd.C₇ -C₁₈-alkyl .Iaddend.which is unsubstituted or a C₃ -C₁₈ alkyl which is monosubstituted by a C₁ -C₁₈ -alkoxy or halogen andR² and R³ are eachhydrogen or a C₁ -C₄ -alkyl, and A is nitrogen or CR⁴, where R⁴ ishydrogen, a C₁ -C₄ alkyl or halogen.
 2. A process for combatting fungi,wherein the fungi or the materials, plants, soils or seeds to beprotected against fungus attack are treated with a fungicidallyeffective amount of an aminoazolopyrimidine of the formula ##STR13##where R¹ is a C₄ -C₁₈ -alkyl which is unsubstituted or mono substitutedby a C₁ -C₁₈ -alkoxy or halogen or is aralkyl where the alkyl is of 1-12carbons which is unsubstituted or substituted in the aryl moiety by C₁-C₄ -alkyl, C₁ -C₄ -alkoxy or halogen,R² and R³ are each hydrogen or aC₁ -C₄ -alkyl, and A is nitrogen or CR⁴, where R⁴ is hydrogen, a C₁ -C₄-alkyl or halogen.
 3. The compound of claim 1 wherein R¹ is n-C₈ H₁₇, R²is CH₃, R³ is CH₃, R⁴ is H and A is CR⁴.
 4. The compound of claim 1wherein R¹ is n-C₈ H₁₇, R² is CH₃, R³ is H and A is N.
 5. The compoundof claim 1 wherein R¹ is n-C₉ H₁₉, R² is CH₃, R³ is H and A is N.
 6. Thecompound of claim 1 wherein R¹ is n-C₉ H₁₉, R² is CH₃, R³ is CH₃ and Ais N.
 7. The compound of claim 1 wherein R¹ is an unsubstituted alkyl of7 to 10 carbon atoms.